Pyrazolone azo-dyestuffs insoluble in water



United States PateneO 2,742,458 PYRAZOLONE AZO-DYESTUFFS INSOLUBLE 1N ""WATER GerhardLangbein,.Hdfheim, Germanygassignorrtoliarbwerke .Hoechst Aktiengesellschaft vormals Meister Lucius und BrlillingiFraukfurt am Main-Hochst, Gery, a comp n -G a N Drawings Application June 2, 1952,

Seria1|,No.291,285 1 Claims'prioritmapplication Germany-June 2, 1951 5 Claims. (01. 2609159) The present-invention relates to. azo-dyestufis insoluble in water and to fiber dyed therewithymore particularly, it

relates &to dyestufls of the general for 'ula R1 ,9, it

wherein R and R1 represent aromatic radicals free from' groups impartingtsolubility in water, and X represents hydrogen or a substituent not imparting solubility in water.

In the production of azo-dyestuffs on'the fib'er :by the ice-color method arylides-of 2,3-hydroxynaphthoic acid are known to be the most important and the most-commonly :used groundingcomponent; By means of-these arylides it is possible to produce nearly all :tints ranging from orange to blue by coupling them withidiazo-compounds. However, it has not hitherto been possible to produce useful green dyeings with the aid of these arylides. This needhasEbeen fulfilled to a cer'tain'extent only by the discovery that 2,3-hydroxy-anthracenecarboxylic acid arylides when :coupled with the soc'alled blue bases,yield'blue greengdyeings (see German Patent No. 549,983). V a

Now I have found that on the basisof the 2,3-hydroxynaphthoic acid, newmand valuable water-insolubleazodyestulfs some of which yield green tints can'beobtain'ed by coupling in substance, on the fiber or on a substratum adapted for the production of lakes '2,3- hydroxynaphthoic acid arylides obtainable by condensing 2,3-hydroxynaphthoic acid with'amino azo-dyestufis of the pyrazolone series, and correspondingto the general formula wherein R represents an aromatic radical'free from groups imparting solubility in water, and X represents hydrogen or a substituent'not imparting solubility in water,-with a diazo-cornpound free from groups imparting :solubility in water or with a dia zo-azo-cornpound.

When produced in substance, the new dyestuffs serve for the preparation'of valuable pigments. It is especially advantageous to produce the new insoluble dyestuffs on the fiber by dyeing or printing processes suitable for the production of ice colors. e,

As compared with the corresponding azo-dyestuifs from 2,3-hydroxynaphthoicacid anilide, the tints of the new dyestuifs are generally displaced towards yellow.

For example, bases which produce scarlet tints with the 2,3-hydroxynaphthoic'acid aniline yieldorange tints with arylides used-in the present invention; -red basesyield scarlet tints; current and violet-bases yield hrown' tints; and the ordinary commercial blue bases yield currant, grey blue toolivetints. Many ofthese dyeings possess very 'goodfastness to light and properties of wet fastness. Of special interest are the coupling productsofthese new 2,3-hydroxynaphthoic acid arylides with the dia'zoazo-compou'nds of-arnines, for example, those of the general-formula NH: wherein the nuclei A and B vmay contain substituents, because valuable (green .dyeings can be produced with these dyestuffs. In numerous cases much more'y'ellowish green tints are produced than in the case of themost greenish dyestuif hitherto used in practice from 2,3- h'ydroxyanthracene carboxylic acid-ortho-toluidide and diazotised 3-methoxy 4 aminodiphenylamine, which yields blue-green tints. As regards fastness to light the new dyestuffs are not inferior to the hitherto known 'dyestufis, and-they possess very good properties of wet fastness.

There may also be'usedas diam-components diazoale-compounds of the above formula in which the nucleus B contains a sulfonic acid group. The green dyeings produced with the resulting dyestuifsrhave good properties of wet fastness notwithstanding the presence of the sulfonic acid group. In some cases the dyestuffs containing sulfonic acid groups areeven somewhat clearer'an'd have a better fastness'to chlorinethanthedyestuifs which are free'from sulfonic acid groups and the known green dyestuffs obtainable by using 2,3-hydroxyanthracene carboxylic acid arylides.

--In view of thelarge number of possible coupling combinat'ions the new dyestuffsconstitute a valuable-enrichment ofthe class of pigment dyes and ice colors, especially among green'water-insoluble azo-dyestufis.

. The 2,3-hydroxynaphthoicacid arylides of the above general formula used-as couplingcomponents can be obtained by condensing 2,3-hydroxynaphthoic acid or a functional acid derivative thereof with an amino-'azo- Patented Apr. 17, 1956 (obtainable by condensing 2,3-hydroxynaphthoic acid with l-(3-aminophenyi) 3 methyl-4-(2-methoxy-5"- chlorobenzene-l-azo)--pyrazolone are stirred with 150 parts of alcohol and 40 parts of sodium hydroxide solution of 38 B. until dissolution occurs. The mixture is then poured into 1000 parts of water and the arylide is precipitated from the clear dark yellow solution by acidifying with dilute acetic acid. 250 parts of a very weakly acid solution of 4-nitrobenzene-l-diazoniurn chloride, corresponding to 13.8 parts of l-amino-4-nitrobenzene, are then run at room temperature in the course of a few minutes into the suspension, while stirring. Stirring is continued for minutes, the mixture is filtered with suction, and the residue is washed with water until a neutral reaction is attained. The dyestuff so obtained is a scarlet pigment and has a good fastness to light.

A green pigment dyestuif is obtained by using, instead of the 4nitrobenzene-1-diazoniurn chloride, the diazocompound from 1-amino-4-(2'-methoxy-5-nitrobenzenel'-azo)-2-ethoxy-naphthalene, and preferably working with the addition of a small quantity of pyridine.

EXAMPLE 2 1 part of the arylide obtainable from 2,3-hydrox naphthoic acid and l-(3'-aminophenyl)-3-methyl-4- (2"-methyl-4"-chloro-benzene-1"azo)-5-pyrazolone, and corresponding to the formula is stirred, while gently heating, with 3 parts of alcohol, 3 parts of water and 0.6 part of sodium hydroxide solution of 38 B. until dissolution is complete and then poured into a mixture of 983 parts of water, 7 parts of sodium hydroxide solution of 38 B. and 10 parts of Turkey red oil. A clear yellow solution is obtained. 50 parts of cotton yarn are introduced into the bath thus produced and treated therein for /2 hour at 30 C.- 35 C., while frequently working the yarn in the bath. After squeezing and centrifuging the yarn, it is placed in a bath containing in 1000 parts of water, 4 parts of a dyeing salt consisting of 33 per cent of the diazonium chloride of l-amino-4-(2,4-dimethoxy-5-nitro-benzene- 1'-azo)-2-ethoxynaphthalene in addition to aluminium sulphate and sodium sulphate. The dyeing is developed for -20 minutes at 30 C. After being rinsed the material is soaped twice at the boil for 10 minutes on each occasion with a solution which contains in 1000 parts 50 parts of a soap solution of 1:20 strength and 4 parts of a sodium hydroxide solution of 38 B.

An intense, clear green dyeing is obtained which has very good properties of wet fastness and a good fastness to light.

By carrying out the development with the same molecular proportion of diazotised 1-amino-4-(2-n1ethyl-5- nitrobenzene-l'-az0) 2 ethoxynaphthalene-o-sulphonic acid in a bath rendered feebly alkaline, for example, by the addition of a little pyridine, a similar, somewhat clearer and more bluish-green tint is produced which likewise possesses good properties of wet fastness but has a better fastness to chlorine than the dyeing previously described.

With other diazotised amines and other 2,3-hydroxynaphthoic acid arylides of the above constitution dyestuffs are obtained having similarly good properties of wet fastness and a good to very good fastness to light.

In the following table are given a number of other water-insoluble azo-dyestufls of this invention:

Table Diazo component Coupling component Tint (1) 1-amino-2, 5-dichiorobenzene.

(2) l-aminoanthraquinone...

(9) 1-amino-4-chloro-4- methyl-benzene.

(l0) 1-aznino-4-nitro-2- methoxybenzene.

(i1) 1amino-4-benz0y1- amino-2,5-diethoxy-benzene.

(12) t-amino-ti-mothoxy diphcnylarnnle.

(13) 1-amino-4-(4-nitrobenzene-1azo)-2 5-dimethoxybenzene.

(14) l-am inc-k (2 5'-dichlorobenzene-1'-azo)-2- methoxy naphthalene 6 sulphonic acid.

(15) 1-amino-4-(2-methoxy- 5' -nitrobenzene-1 -azo) -2- ethoxynaphthalene.

(16) l-amino-4-(2-mctl1yl-5- nitrohenzene 1 -'azo) 2 ethoxwnaphthaiene-o-sulphonic acid.

azo) -2-etl1oxynapht halene.

(18) l-amino-2-(4-n1tro-2- chlorobenzene l azo) 5 methoxy 4 methyiben zone.

(19) i-arnino-4-(2'-methoxy- 5-nitrobenzene-1-azo) -2- methoxynaphthalene 6 snlphonic acid.

(20) 1 amino 2,5 dichloro benzene (21) 4-alninodiphenylamine.

(24) 1 -amino-4-(2'-methy1- 5-nitrobenzene-1-azo) -2- ethoxynaphthalene-fi-sulphonic acid.

(25) 1-am1no-4-(2-methoxy- 5-nitrobenzene-l'-azo) -2- ethoxynaphthalene.

C ondensation product from 2,3-hydroxynaphthoie acid and ,1-(3- aminophenyD-B-methyi- 4-(2"-methyl-4"-chlorobanzene-1"-azo)-5' pyrazolone.

, do -.do

Condensation product from 2,3-hydroxynaphthoic acid and 1-(3'- aminophenyD-B-methyl- 4-(3-chlorobenzene-1- nzg)-6-pyrazoione.

Condensation product trom 2,3-hydroxynaphthoic acid and 1-(3- aminophenyl) -3-methyl- 4 (2" methow 5" chlorobenzene-1"-azo) fi-piyrazolone.

Condensation product from 2,3-hydroxynnphthoic acid and 1-(4-aminophenyl) 3- methyl 4 (3 chlorohenzene -1 azg)-5-pyrazolone.

Condensation product from 2,3-hydroxynaphthoic acid and 1-(3-aminophenyl) -3-methy1-4- (2"-trifluoromethy1-4- chlorobenzene-l -azo) fi-piyrazolone.

Condensation product from 2,3-hydroxynaphthoic acid and 1-(3-aminophenyl) -3-methyi-4- (naphtha1ene-1-a zo) -5- pyrazolone.

Condensation product from 2,3-hydroxynaphthoic acid and 1- (3-amincphenyl)-3-carbethoxy- 4- (2 -methyi-4 -cl11orobenzene-1'azo)-5-pyrazolone.

scarlet Do. curt-ant.

grey-blue.

J brown. 1

clear green.

olive green.

orange scarlet.

red.

violet-grey.

grey-blue.

black in a :hick dye blue green.

clear green.

green.

brown.

dark green.

scarlet.

dark olive.

blue green dark-green.

grey-blue.

grey-green.

stands for a member of the group consisting of hydrogen and the sulfonic acid group.

3. The water-insoluble azo-dyestulf corresponding to the following formula I claim: 1. The water-insoluble azo-dyestutfs corresponding to the following general formula:

f: 1111 N02 N I p- 0011,

N A Y I O.alkyl I H 002115 N the following general formula R2 IITFOOCHI 1LT N I OCH;

4. The water-insoluble azo-dyestufi corresponding to 25 the following formula 00in, O.alkyl N C OH OH N t 40 N C O-NH- wherein R and R2 stand for radicals of the benzene series 5. The water-insoluble azo-dyestuif corresponding to free from sulfonic and carboxylic acid groups and Y the following formula N0: Ha

Krzikalla et al. July 2, 1934 Sexton July 20, 1937 

1. THE WATER-INSOLUBLE AZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA: 